Polymers of alkenyl phosphorus esters



United States Patent 3,243,417 POLYMERS F ALKENYL PHOSPHORUS ESTERSPeter Kirby, Kelsall, England, assignor to Shell Oil Company, acorporation of Delaware No Drawing. Original application Oct. 4, 1960,Ser. No. 60,303, now Patent No. 3,166,505. Divided and this applicationNov. 13, 1964, Ser. No. 411,142 Claims priority, applicatiozn G/r6e61tBritain, Jan. 29, 1960,

Claims. (Cl. 260-86.1)

This patent application is a division of copending patent applicationSerial No. 60,303, filed October 4, 1960, and which matured as US.Patent 3,166,505 on January 19, 1965.

This invention relates to oil-soluble copolymers of analkenyl-substituted phosphorus compound containing a phosphinylidynegroup and at least one polymerizable phosphorus-free mono-olefinicallyunsaturated compound having an olephilic hydrocarbon chain of at least 8carbon atoms. Preferred monomers to be copolymerized with the phosphoruscompounds are mono-olefinically unsaturated polar-containing compoundshaving an eleclphilic hydrocarbon chain of at least 8 carbon atoms.

A further feature of the present invention relates to oil-solublecopolymers comprising a dialkenyl-substituted phosphorus compoundcontaining a phosphinylidyne group and at least one phosphorus-freepolymerizable mono-ole finically unsaturated compound having anelecphilic hydrocarbon chain of from 8 to 30 carbon atoms. The termphosphinylidyne group is to be construed throughout the presentspecification as meaning EP O group (cf. Iour. Chem. Soc, 1952, page5125).

The dialkenyl-substituted phosphorus compounds containing aphosphinylidyne group may be derived from phosphoric acid, phosphonicacid, phosphinic acid or phosphine oxide. Thus, a very suitable class ofphosphorus compounds is that having the general formula:

Rio

R2O/ O a where R, and R are alkenyl or cyeloalkenyl radicals and R isa'hydrogen atom, or an alkyl, cycloalkyl, aryl, aralkyl or alkarylradicals. R and R may be (1: 3 monoolefinically unsaturated hydrocarbonradicals, e.g. vinyl or aor fi-allyl substituted vinyl radicals, butpreferably R and R are 18: mono-olefinically unsaturated hydrocarbonradicals of the formula --CR' 'CR=CR where R is a hydrogen atom or analkyl group preferably having no more than 6 carbon atoms. R, and R maybe the same or different, but are preferably the same, and morepreferably they are allyl radicals. Dialkenyl esters of phosphoric acidmay be prepared by any method wellknown in the art. For example, thevinyl type esters may be prepared by di-hydrohalogenation of compoundsof the formula (XCHgCHzO) R(3 n)P O where X is halogen, which compoundsmay be themselves prepared by reacting phosphorus chlorides withethylene oxide.

The allyl type esters can be prepared by reacting the desiredphosphorodichloridate with a flt'y mono-oleo'finically unsaturatedalcohol in the presence of an acid sequestrant, e.g., pyridine. Examplesof suitable phos phoric acid esters are diallyl hydrogen phosphate,diallyl methyl phosphate, diallyl phenyl phosphate, diallyl cyclohexylphosphate, allyl methallyl hydrogen phosphate, diviny hydrogenphosphate, divinyl phenyl phosphate, bis- (Z-ethylallyl) hydrogenphosphate, di-methallyl benzyl phosphate, dicrotyl hydrogen phosphate,bis(2-pentenyl) hydrogen phosphate and -bis(2-hexenyl) isopropylphosphate.

A further class of phosphorus compounds useful as monomers in thepresent invention is that havlng the general formula:

where any of the two groups R R and R are alkenyl or cycloalkenyl groupsand the other group is hydrogen, alkyl, cyoloalkyl, ary-l, alkaryl, oraralkyl. Preferably R and R are alkenyl or cycloalkenyl radicals. Thealkenyl radicals may be 11:5 m-ono-olefinically unsaturated hydrocarbonradicals, e.g., vinyl or on or fi-allyl substituted vinyl radicals, butpreferably the alkenyl radicalsare 5: mono-olefinically unsaturatedhydrocarbon radicals of the formula OR' -CR=CR' where R is a hydrogenatom or an alkyl group preferably having up to six carbon atoms. Thealkenyl radicals may be the same or different but are preferably thesame, more preferably they are allyl radicals. The above dialkenylderivatives of phosphonic acid may be prepared by. any of the methodswell-known in the art. For example, if R and R are alkenyl radicals, thedialkenyl phosphonates may be conveniently prepared by reacting thedesired phosphonic dih-alide with the desired mono-oletinicallyunsaturated alcohol in the presence of an acid sequestran-t, e.g.,pyridine to produce the diester. When R and R are dialkenyl radicals,the desired compounds may be prepared by an Arbuzov reaction on adialkyl alkenyl phosphite with an alkenyl halide.

Examples of suitable dialkenyl derivatives of phosphonic acid arediallyl phenylphosphonate, diallyl ethylphosphonate, divinylethylphosphonate, the monoallyl ester of allylphosphonic acid, allylmethallyl phenylphosphate, dicrotyl phosphonate, diallylbenzylphosphate, divinyl phenylphosphonate and di(2-pen-tenyl)ethylphosphonate.

A further class of dialkenyl phosphorus monomers that may be used informing the copolymers of the present invention has the general formula:

In R;

where two of the groups R R and R are alkenyl or cycloalkenyl and theother group is hydrogen, alkyl, cycloalkyl, -aryl, aralkyl or alkaryl.Preferably R is an alkenyl or cycloalkenyl radical. The alkenyl radicalsmay be on}? Inono-olefinically unsaturated hydrocarbon radicals, e.g.,vinyl or aor fi-allyl substituted vinyl radicals, but preferably thealkenyl radicals are 5: monoolefinically unsaturated hydrocarbonradicals of the formula -CR' -CR'== CR where R is a hydrogen atom or analkyl group preferably having up to six carbon atoms. The alkenylradicals may be the same or different but are preferably the same, morepreferably they are allyl radicals. The above dialkenyl derivativesof'phosphinic acid may be readily prepared by any of the methods knownin the art.

If R is alkenyl the [9:7 mono-olefinically unsaturated derivatives maybe prepared by direct esterificaticnof an alkenyl phosphinic acid withthe desired Bry mono-olefinically unsaturated alcohol. Alternatively ifR is alkenyl and both alkenyl radicals in the product are to be thesame, a convenient method of preparation is to react a phosphonousdichloride with the desired flz'y monoolefinically unsaturated alcoholto form the diester of a phosphinous acid which partially undergoes anArbuzov re-arrangement to form the ester of the corresponding phosphinicacid which may be separated from the reaction mixture by distillation.

If R, and R are both alkcnyl radicals, the desired 'product may beobtained by reacting a phosphorodihalidate of the formula ROP(O)X withan alkenyl Grignard reagent, e.g., RMgBr (R' is alkenyl) to formROP(O')R' Examples of dialkenyl derivatives of phosphinic acid are theallyl esterv of phenyl-prop-2-enyl-phosphinic acid, the allyl ester, ofprop-2-enyl phosphinic acid, the vinyl ester of vinylphenylphosphinicacid, diallyl phosphinic acid, allylmethallylphosphinic acid, ethyldiallylphosphinate, phenyl divinylphosphin'atc and methylallylmethallylphosphinate.

A still further class of dialkenyl phosphorus compounds useful in thepresent invention is that having the general formula:

112 R; p where R and R are alkenyl or cycloalkenyl radicals and R is ahydrogen atom or an alkyl, cycloalkyl, aryl, aralkyl, or alkarylradical. olefinically unsaturated hydrocarbon radicals, e.g., vinyl oraor fl-alkyl substituted vinyl radicals, but preferably R and R are 517mono-olefinically unsaturated. hydrocarbon radicals of the formula -CR'CR'=CR where R is a hydrogen atom or an alkyl group preferably having upto six carbon atoms. R and R may be the same or different, butpreferably they are the same and more preferably they are allyl groups.Such phosphine oxides may readily be prepared by the reaction between adihalophosphine and the desired alkenyl Grignard reagent followed by airoxidation. Exemplary of suitable phosphine oxides are diallyl phenylphosphine oxide, divinyl phenyl phosphine oxide, diallyl ethyl phosphineoxide, diallyl benzyl phosphine oxide, allyl methallyl phenyl phosphineoxide, dimethallyl phenyl phosphine oxide and' dimethallyl isopropylphosphine oxide.

Mixtures of two or more of the foregoing monomers can be used ifdesired.

Typical of the other polymerizable mono-olefinically unsaturatedcompounds having an oleophilic hydrocarbon chain of at least 8 carbonatoms with which the foregoing phosphorus compounds may be copolymerizedare acrylic acid and tit-substituted acrylic acids and theirderivatives, such as their esters, nitriles and amides. Examples of suchcompounds are C alkyl substituted ethacrylic acid, a-dicresyl acrylicacid, the alkyl esters thereof, e.g., octyl, nonyl, lauryl, cetyl,oleyl, stearyl and dimethylcyclohexyl esters, u-ethylhexylacrylamide,laurylacrylamide, a-octacrylonitrile, 2-butyl-2-hexenenitrile,2-propyl-2-octenenitrile, 2-chloroethyl-2-hexenenitrile,2-ethyl-3-chloro-2-hexenenitrile, 2-isopropyl-3-bromo-2-cotenenitrile,and a-OC- tyl-fi-cy-clohexylacrylonitrile.

Other compounds which may be used to form'the copolymers used in thepresent invention are vinyl esters of organic acid such as vinyllaurate, vinyl stearate, vinyl ethers such as vinyl octyl ether, vinyllauryl ether, vinyl dicresyl ether, vinyl ketones such as octyl vinylketone, lauryl vinyl ketone, and stearyl vinyl ketone, vinyl arylcompounds such as ortho-octyl styrene, para-lauryl styrene, para-stearylstyrene, a-octyl styrene and other alkyl derivatives of styrene in whicha C alkyl group or groups may be substituted in the ring or in the sidechain or both. Allylesters, ethers and ketones corresponding to thevinyl compounds listed above may also be used. 11,13- unsaturatedpolycarboxylic acids and their derivatives such as maleic, fumaric,citraconic, itaconic, crotonic, aconitic and tricarballylic acids andtheir mono-polyesters with aliphatic and aromatic alcohols, and theiramides an nitriles, may also be used.

Other compounds which maybe used to form the phosphorus-containingcopolymers used in the present invention are the a-olefins particularlythose having more than 8 and preferably 12-20 carbonatoms,amino-substi-.

tuted olefins, e.g., p-(fl-dioctylaminoethyl)styrene andnitrogen-containing heterocyclic compounds having a monoolefinicallyunsaturated substituent, e.g., the vinyl pyridines (Whether 2-, 3- or4-substituted) and the vinyl alkyl pyridine, 3-lauryl-5-vinyl pyridine,4-lauryl-2-vinyl pyridine, 4-steary1-2-vinyl pyridine and2-stearyl-5-vinyl pyridine. Vinyl lactams are also suitable monomers,particularly the N-vinyl pyrrolidones or N vinyl piperidones. Thesevinyl compounds should have at least one C alkyl radical in themolecule.

Of the above listed monomers copolymerizable with thephosphorus-containing monomers according to the R and R maybe (125monopresent invention, it is preferred that they contain at least oneoleophilic hydrocarbon chain of at least eight carbon atoms which ispreferably an alkyl radical of 12 to 20 carbon atoms, and suchcopolymers per se are a feature of the present invention. Mixtures ofthe above monomers maybe used in forming the copolymers used inlubrieating oil additives according to the present invention.Particularly preferred. copolymers are those formed fromdialkenyl-substituted phosphorus compounds with a higher alkyl ester ofan acrylic or methacrylic acid, i.e., where the ester group contains 8or more carbon atoms, e.g., lauryl methacrylate. Minor proportions oflower alkyl esters of acrylic or methacrylic acids, e.g., methylmethacrylate, may advantageously be present in such copolymers.

The molar ratio of phosphorus-containing monomer to the polymerizablecomonomer may vary with wide limits and generally lies between 20:1 and1:20. Preferably the ratio lies between 1:1 and 1:20, with ratiosbetween 1:3 and 1:10 being especially suitable.

The copolymers of this invention can be prepared by any suitable means.Normally the reactants are copolymerized in the presence of a catalyst.Oxygen-yielding catalyst, such as organic peroxides may be used. Thesemay be aliphatic, aromatic, heterocyclic, or alicyclic peroxides, suchas diethyl peroxide, tertiary butyl hydroperoxide, di(tertiary butyl)peroxide, benzoyl peroxide, di-

methyl thienyl peroxide, dilauroyl peroxide and urea peroxide. Othercatalysts include sodium bisulphite, diethyl sulfoxide, ammoniumpersulfate, alkali metal perborates and. azo compounds, e.g.,azo-(bis-isobutyro) nitrile. The catalysts are generally used in anamount of 0.1 to 5% by weight of the reactants.

The copolymerization reaction may -be carried out under a variety ofconditions. For example, the reaction can be carried out in the presenceor absence of an inert solvent, such as a hydrocarbon, under a blanketof nitrogen or carbon dioxide and at a temperature varying from roomtemperature or lower to about 180 C. or higher for a period of fromabout 2 to 48 hours. 7

It is preferred that the reaction be carried out in such a way that theresulting copolymer has a molecular weight above 50,000 and preferablybetween 75,000 and 1,000,- 000.

The following examples illustrate methods of producing copolymers of thepresent invention.

EXAMPLE 1 A solution of 277 g. of allyl alcohol and 326 g. pyridine in280 ml. of ether was cooled to approximately 30 C. by means of a bath ofIPA/CO and was then added to a solution of 255 g. phosphorus oxychloridein 132 ml. ether over a period. of two hours. After the first hour afurther ml. of ether was added to facilitate stirring. The reactionmixture was stirred for a further three hours after which-time thepyridinium chloride formed was filtered off. The filtrate was evaporatedleaving triallylphosphate as a clear yellow oil.

51 grams ofthe triallylphosphate was dissolved in 100 ml. of I.M.S. andrefluxed with 100 ml. of 5 N aqueous solution hydroxide for two hours.The solvents were then removed under reduced pressure (100 C./ 15 mm.)and the residual oil was extracted with ether in ordcrtO removeunhydrolyzed phosphate. The oil was then treated with dilutehydrochloric acid until acid and the oil thus separated was extractedwith ether and produce diallyl hydrogen phosphate.

A mixture of 3.4 g. of the diallyl hydrogen phosphate and g. of laurylmethacrylate in 15.5 g. of technical white oil and 20 ml. of benzene wastreated with 0.5 benzoyl peroxide and treated at 70 C. for 18 hours withstirring. The benzene was then evaporated to leave the copolymer as aviscous, oil-soluble product. The molar ratio of the diallyl hydrogenphosphate to lauryl methacrylate in the copolymer was 1:6.

EXAMPLE 2 Phenylphosphonous dichloride was prepared by refluxingtogether 525 ml. phosphorous trichloride, 468 ml. benzene and 300 g. ofaluminum chloride for four hours. Phosphorus oxychloride (223 ml.) wasthen added and the mixture briefly refluxed. Excess benzene andphosphorous trichloride was evaporated under vacuum and the residuecooled to about 40 C. and extracted with ligroin. From the extract,crude phenylphosphonous dichloride was recovered and purified byredistillation under reduced pressure.

A solution of 60.5 g. of allyl bromide in 285 ml. ether was addeddropwise to 12 g. magnesium in 100 ml. ether. After stirring for 1 hour,23 g. of phenylphosphonous dichloride in 100 ml. of ether was added andthe mixture stirred overnight. A solution of 50 g. of aluminum chloridein 250 ml. water was added and the ethereal layer was separated, driedover sodium sulfate and evaporated.

The resultant crude diallylphenylphosphine was purified byredistillation. All these operations were conducted in a nitrogenatmosphere.

5.5 grams of the tliallylphenylphosphine was dissolved in 12 ml. ofbenzene and air passed through the solution for thirty minutes toproduce diallylphenylphosphine oxide. To this solution was added 23 ml.benzene, 15 g. of technical white oil, 7 g. of lauryl methacrylate and0.5 g. of benzoylperoxide. The mixture was heated to 75 C. and stirredfor 24 hours. At the end of each of the first three hours, a furtheramount of 7 g. lauryl methacrylate was added and with the thirdaddition, a further 0.5 g. of benzoyl peroxide was added. The benzenewas evaporated at reduced pressure and the residue heated at 100 C./lmm. Hg for minutes. The resulting copolymer "solution ofdiallylphenylphosphine oxide and lauryl methacrylate in technical whiteoil was soluble in mineral oil. The molar ratio ofdiallylphenylphosphine oxide to lauryl methacrylate was 1.4.

EXAMPLE 3 Phenyl phosphonous dichloride (prepared as in Example 2, 90g.) was dissolved in carbon tetrachloride (500 ml.) and the whole cooledto -50 C. by a cardice/ IPA coolant. Dry chlorine gas was not bubbledinto the solution until the exothermic reaction was complete. Theproduct was filtered while cool to give a residue of phenyl phosphonictetrachloride. Further quantities of this material were obtained byevaporation of the mother liquors. The product was purified byrecrystallization from carbon tetrachloride, followed by drying in avacuum desiccator.

Phenyl phosphonic tetrachloride (63 g.) was dissolved in benzene (250ml.) and the stirred mixture treated with sulfur dioxide until reactionwas complete. The reaction is rapid and the phenyl phosphonic dichloridePh.POCl produced was recovered by distillation B.P. 87 C./l mm. Hg.Phenyl phosphonic dichloride (49 g.) was added slowly with stirring to asolution of allylalcohol (29 g.) and pyridine g.) in ether (250 ml.)cooled to 0 C. The rate of additionwas such that the temperature of themixture remained at 0 C. Stirring was continued for 2 hours aftercomplete addition. The reaction product was filtered to remove pyridinehydrochloride and the residue washed with 200 ml. ether. The ether wasevaporated from the filtrate and the residue distilled to givediallylphenylphosphonate B.P. 112 C./0.3 mm. Hg.

To a solution of diallylphenylphosphate (5.9 g.) and lauryl methacrylate(25.4 g.), ditert-butyl peroxide (0.4 ml.) was added and the wholestirred vigorously. The solution was maintained under these conditionsfor 5 hours. The product had a molar ratio of 1!:4diallylphenylphosphonate to lauryl methacrylate and was a 66.7%concentration in mineral oil. This concentrate was readily soluble infurther samples of mineral oil.

EXAMPLE 4 To a solution of allylalcohol g.) and pyridine (168 g.) indiethyl ether (2000 ml.), phenyl phosphonous dichloride was added slowlywith stirring. The rate of addition was adjusted to maintain-a gentlereflux. Stirring and refluxing were continued for a further two hoursafter complete addition. Pyridine hydrochloride was filtered off and theresidue washed with more ether (500 ml.). The ether was evaporated fromthe filtrate and the product distilled, the bulk of the material(allylphenyl-prop-2-enyl-phosphinate) boiling at 102 C./0.4 mm. Hg.Small amounts of diallyl phenylphosphonite are separated during thedistillation B.P. 79 C./0.4 mm. Hg.

To a solution af allyl-phenyl prop-2-enyl-phosphinate (6 g.) and laurylmethacrylate (28 g.) in mineral oil (68 g.) at -5 C. di-tert-butylperoxide (0.4 ml.) was added and the whole stirred vigorously for 24hours. The product was heated at 100 C./0.5 mm. Hg for 30 minutes but nodistillate was obtained. This product had a 1:4 molar ratio ofallyl-phenyl-prop-2-enyl-phosphinate to lauryl methacrylate and was a33.3% concentrate in mineral oil.

Other oil-soluble copolymers of this invention in the molecular weightrange of from 100,000 to 800,000 include:

Diallyl phenyl phosphate/a-octyl acrylamide, diallylcyclohexylphosphate/vinyl laurate, dimethallyl hydrogen phosphate/laurylmethacrylate, diallyl phenyl phosphate/ vinyl laurate, divinylethylphosphonate/a-octyl acrylonitrile, dimethallylethylphosphonate/oleyl maleate, allylprop 2 enyl phosphinate/laurylmethacrylate, diallyl phosphinic acid/stearyl methacrylate, divinylphenyl phosphine oxide/stearyl methacrylate, dimethallyl phenylphosphine oxide/Z-octyl-S-vinyl pyridine and diallyl ethylphosphineoxide/lauryl methacrylate.

The lubricating .oil in the lubricating compositions of the inventioncan be any natural or synthetic oil having lubricating properties. Thus,the oil can be a hydrocarbon lubricating oil obtained from paraflinic ornaphthcnic crude or mixtures thereof. The viscosity of these oils mayvary over a wide range, such as from 100 SUS at 100 F. to 100 SUS at 210F. The hydrocarbon lubricating oil may be blended with fatty oils suchas castor oil or lard oil, and/or with synthetic lubricating oils suchas polymerized olefins, copolymers of alkylene glycols and alkyleneoxides, organic esters, e.g., di(2-ethylhexyl) sebacate, dioctylphthalate and trioctyl phosphate and polyalkyl silicone polymers such asdimethyl silicone polymers. If desired, the synthetic lubricating oilsmay be used as the sole base lubricating oil or admixed with fatty oilsor derivatives thereof.

In the lubricating compositions of the natural and/or synthetic varietythe polymeric additive may be present in a minor proportion by weightbased on the total composition, generally from 0.01% to 20% andpreferably from 0.1% to 8% by weight. Such lubricating compositions maybe modified by the addition thereto of minor proportions of otheradditives such as metal dithiophos phates, e.g., zincdi-Z-ethylhexyl-dithiophosphate, metal organic sulfonates, e.g., neutralor basic calcium, barium or zinc petroleum sulfonate; metalthiocarbonates, e.g., zinc, chromium or calcium dibutyl or diamyldithiocarbamate; amines, e.g., phenyl-alpha-naphthylamine oroctadecylamine; alkylatcd phenols and alkylated bisphenols, e.g.,2,G-ditertiary-butyl-4-methylphenol, 2,6-ditertia1ybutyl-4-hydroxybenzylalcohol and 4,4'-methylenebis(2,6-ditertiarybutyl phenol) organic sulfides, e.g.,dibenzyldisulfide.

Lubricating compositions of the present invention are useful as engineoil, gear oils, turbine oils and various other fields of lubricationwhere detergency, viscosity index and load carrying properties areessential.

Compositions of this invention are illustrated by the followingformulations; the ratios .in brackets being the mole ratios of themonomers used for preparing the copolymers. The mineral lubricating oilused is an oil having a viscosity of cs. at 210 F.

Composition A: Percent by weight Copolymer of diallyl hydrogenphosphate/ lauryl methacrylate (1:6) 4 Mineral oil Balance CompositionB:

Copolymer of diallyl hydrogen phosphate/ lauryl methacrylate (1:8) 4

Mineral oil Balance Composition C:

Copolymer of diallyl phosphine oxide/ lauryl methacrylate (1:4) 3.5Mineral oil Balance Composition D:-

Copolymer of allyl ester of phenyl-prop-2- enyl phosphinic acid/laurylmethacrylate 1:4 2.7 Mineral oil Balance Composition E: i

Copolymer diallyl phenyl phosphonate/ lauryl methacrylate (1:4) 6.8Mineral oil Balance Composition F:

Copolymer of diallyl phenyl phosphine oxide/lauryl methacrylate (1 :4)3.9 4,4 methylenebis(2,6 ditertiarybutyl-- phenol) 0.75 Mineral oilBalance In order to illustrate the properties of lubricatingcompositions according to the p 'esent invention, certain compositionswere subjected to ests in the following manner.

The thickening ability of the copolymers used as additives in thepresent invention was assessed in terms of the VT coefficient,calculated from the formula:

--nasza zmTl V T "laud...

100 F. 100 F. 7mm: new oil 100 F. base oil where 1 is the viscosity.

Various copolymers were added to'a base mineral lubricating oil having aviscosity of 10 cs. at 210 F. and the VT values determined from theabove equation. The results are contained in Table I.

These figures represent good thickening properties. The dispersantproperties of various compositions were illustrated in the followingmanner.

1 part by weight of used straight mineral oil containing about 2% wt. ofoil-insolubles. from a diesel engine was mixed with 5 parts of theunused mineral oil of Compositions A-F. In this blend the insolubleparticles are clustered. Other blends are made containing, as before, V6of used oil, and the remaining /6 a series of increasing concentrationsof one of the additives in the unused mineral oil. At a particularconcentration the insoluble particles became dispersed, and thisconcentration is taken as a measure of the dispersancy of the. additive.Some results are given in Table II.

Table II Concentration of copolymer required to disperse p y clusters inmg. per g. blend Composition F exhibited good low temperatureperformance properties when used in an automotive engine as is evidencedby absence of sludge deposition in the sump. Further, Composition F wassubmitted to an antiscutfing test in an automotive engine in which thecam wear and degree of tappet scufling is indicative of the loadcarrying capacity of the oil. Compared with a similar formulation, butin which the 3.9% of the copolymer according to the invention isreplaced by 4% wt. of a copolymer of lauryl methacrylate and vinylpyrrolidone, Composition F exhibits a 60% reduction in the amount oftappet scufiing and a reduction in cam wear. Also, Compositions A andD,when subjected to a test for extreme pressure properties on the 4-ballmachine, exhibited 2 /2 second seizure delay loads of 137 kg. and 92 kg.respectively comparedwith 65 kg. for the base oil.

I claim as my invention:

1. As a new compound, an oil-soluble copolymer of a dialkenylsubstituted phosphorus compound selected from the group consisting ofdialkenyl phosphate, dialkenyl phosphonate and dialkenyl phosphine oxideand a C alkyl acrylate, in the mole ratio of 1:20 to 20:1 respectively,and having a molecular weight of from about 50,000 to about 1,000,000.

2. The compound of claim 1, wherein the phosphoru compound is adialkenyl phosphate and the mole ratio of the reactants being from 1:1to 1:20, respectively.

3. The compound of claim 1, wherein the phosphorus compound is adialkenyl phosphonate and the mole ratio of the reactants being from 1:1to 1:20, respectively.

4. As a new compound, oil-soluble copolymer of diallyl hydrogenphosphate and lauryl methacrylate in the mole ratio of 1:3 to 1:10,respectively, said copolymer having a molecular weight of from about50,000 to 1,000,000.

5. As a new compound, oil-soluble copolymer of diallyl phenyl phosphineoxide and lauryl methacrylate in the mole ratio of 1:3 to 1:10,respectively, said copolymer having a molecular weight of from about50,000 to 1,000,000.

References Cited by the Examiner UNITED STATES PATENTS 2,659,714 1l/1953Harman et al 252-49.8 2,694,684 11/1954 Rogers ctal. 252-49.8

JOSEPH L. SCI-IOFER, Primary Examiner.

HARRY WONG, Assistant Examiner. I

1. AS A NEW COMPOUND, A OIL-SOLUBLE COPOLYMER OF A DIALKENYL SUBSTITUTEDPHOSPHORUS COMPOUND SELECTED FROM THE GROUP CONSISTING OF DIALKENYLPHOSPHATE, DIALKENYL PHOSPHONATE AND DIALKENYL PHOSPHINE OXIDE AND AC8-20 ALKYL ACRYLATE, IN THE MOLE RATIO OF 1:20 TO 20:1 RESPECTIVELY,AND HAVING A MOLECULAR WEIGHT OF FROM ABOUT 50,000 TO ABOUT 1,000,000.